136146-67-3

Upstream product

• 6973-60-0 1-Methyl-2-pyrrolecarboxylic acid 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 96-54-8 N-Methylpyrrole 
• 696-62-8 para-iodoanisole 
• 141339-54-0 bis(4-anisyl)iodonium triflate 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 623-12-1 4-chloromethoxybenzene 
• 98-68-0 4-methoxy-phenyl-sulphonyl chloride 
• 104-93-8 p-methylanizole 
• 85234-21-5 1-(4-methoxyphenyl)but-3-en-1-one 
• 136146-92-4 p-Methoxyphenyl(3-bromo-2-methoxypropyl)ketone 
• 74-89-5 methylamine 

Downstream Products

• 1080025-57-5 2-(4-methoxyphenyl)-1-methyl-5-(tricyanoethenyl)-1H-pyrrole 
• 1080025-61-1 2-(4-methoxyphenyl)-1-methyl-3-(tricyanoethenyl)-1H-pyrrole 
• 1080025-67-7 2-(4-methoxyphenyl)-1-methyl-4-(tricyanoethenyl)-1H-pyrrole 
• 1245638-76-9 2-(cyclopenta-2,4-dienylidenemethyl)-5-(4-methoxyphenyl)-1-methyl-pyrrole 
• 1049131-61-4 5-(4-methoxyphenyl)-1-methyl-1H-pyrrole-2-carboxaldehyde 

Relevant academic research and scientific papers

Organophotocatalytic Arene Functionalization: C-C and C-B Bond Formation

Organophotocatalytic C-C and C-B bond formation reactions of aryl halides have been developed in the presence of an organophotosensitizer, 3,7-di([1,1′-biphenyl]-4-yl)-10-(4-(trifluoromethyl)phenyl)-10H-phenoxazine that has highly negative reduction potential at its photoexcited state. The developed reaction conditions are mild and allow the intermolecular C-C bond formation of the generated aryl radical with electron-rich (hetero)arenes and C-B bond formation with bis(pinacolato)diboron.

Direct Arylations of Heteroarenes with Benzenesulfonyl Chlorides Using Pd/C Catalyst

The reactivity of heteroaromatics in direct arylation with benzenesulfonyl chlorides using 10 % Pd/C as catalyst was explored. With (benzo)thiophenes, (benzo)furans, pyrroles and selenophenes, high yields in arylated heteroarenes were obtained. These arylations were performed using only 5 mol-% Pd/C and Li2CO3 as inexpensive base. The regioselectivities are similar to those observed with homogeneous palladium catalysts. Better yields were obtained with electron-deficient benzenesulfonyl chlorides than with the electron-rich ones. Notably, useful substituents such as bromo or iodo on the benzenesulfonyl chloride were tolerated, as no cleavage of the C–Br or C–I bonds was observed under these conditions. The use of Pd/C presents several advantages compared to the previously employed homogeneous palladium catalysts, as it can be easily removed by filtration at the end of the reaction. The major side-products of the reaction are HBr associated to Li2CO3. Therefore, this new protocol affords a very attractive synthetic scheme in terms of cost, simplicity and low environmental impact for the access to arylated heteroaromatics.

Polysulfide Anions as Visible Light Photoredox Catalysts for Aryl Cross-Couplings

Polysulfide anions are endowed with unique redox properties, attracting considerable attentions for their applications in alkali metals-sulfur batteries. However, the employment of these anionic species in redox catalysis for small molecule synthesis remains underdeveloped due to their moderate-poor electrochemical potential in the ground state, whereas some of them are characterized by photoabsorptions in visible spectral regions. Herein, we disclose the use of polysulfide anions as visible light photoredox catalysts for aryl cross-coupling reactions. The reaction design enables single-electron reduction of aryl halides upon the photoexcitation of tetrasulfide dianions (S42-). The resulting aryl radicals are engaged in (hetero)biaryl cross-coupling, borylation, and hydrogenation in a redox catalytic regime involving S4?-/S42- and S3?-/S32- redox couples.

Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects

Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.

A case of chain propagation: α-aminoalkyl radicals as initiators for aryl radical chemistry

The generation of aryl radicals from the corresponding halides by redox chemistry is generally considered a difficult task due to their highly negative reduction potentials. Here we demonstrate that α-aminoalkyl radicals can be used as both initiators and chain-carriers for the radical coupling of aryl halides with pyrrole derivatives, a transformation often employed to evaluate new highly reducing photocatalysts. This mode of reactivity obviates for the use of strong reducing species and was also competent in the formation of sp2 C-P bonds. Mechanistic studies have delineated some of the key features operating that trigger aryl radical generation and also propagate the chain process.

Reductive Electrophotocatalysis: Merging Electricity and Light to Achieve Extreme Reduction Potentials

We describe a new electrophotocatalytic strategy that harnesses the power of light and electricity to generate an excited radical anion with a reducing potential of -3.2 V vs SCE, which can be used to activate substrates with very high reduction potentials (Ered ≈ -1.9 to -2.9 V). The resultant aryl radicals can be engaged in various synthetically useful transformations to furnish arylboronate, arylstannane, and biaryl products.

Potent Reductants via Electron-Primed Photoredox Catalysis: Unlocking Aryl Chlorides for Radical Coupling

We describe a new catalytic strategy to transcend the energetic limitations of visible light by electrochemically priming a photocatalyst prior to excitation. This new catalytic system is able to productively engage aryl chlorides with reduction potentials hundreds of millivolts beyond the potential of Na0 in productive radical coupling reactions. The aryl radicals produced via this strategy can be leveraged for both carbon-carbon and carbon-heteroatom bond-forming reactions. Through direct comparison, we illustrate the reactivity and selectivity advantages of this approach relative to electrolysis and photoredox catalysis.

Determination of the inhibitory effects of N-methylpyrrole derivatives on glutathione reductase enzyme

Glutathione reductase (GR) is a crucial antioxidant enzyme which is responsible for the maintenance of antioxidant GSH molecule. Antimalarial effects of some chemical molecules are attributed to their inhibition of GR, thus inhibitors of this enzyme are expected to be promising candidates for the treatment of malaria. In this work, GR inhibitory properties of N-Methylpyrrole derivatives are reported. It was found that all compounds have better inhibitory activity than the strong GR inhibitor N,N-bis(2-chloroethyl)-N-nitrosourea, especially three molecules, 8 m, 8?n, and 8?q, were determined to be the most powerful among them. Findings of our study indicates that these Schiff base derivatives are strong GR inhibitors which can be used as leads for designation of novel antimalarial candidates.

Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation

A new and practical method for the generation of aryl radicals from aryl halides is reported. Rongalite as a novel precursor of super electron donors was used to initiate a series of electron-catalyzed reactions under mild conditions. These transition-metal-free radical chain reactions enable the efficient formation of C-C, C-S, and C-P bonds through homolytic aromatic substitution or SRN1 reactions. Moreover, the synthesis of antipsychotic drug Quetiapine was performed on gram scale through the described method. This protocol demonstrated its potential as a promising arylation method in organic synthesis.

Additive-Free Palladium-Catalyzed Decarboxylative Cross-Coupling of Aryl Chlorides

The cross-coupling of sodium (hetero)aryl carboxylates with (hetero)aryl chlorides proceeds with 1 mol % palladium catalyst and does not require inorganic base, silver salts, or copper salts. This coupling uses two low energy partners, and the only stoichiometric byproducts are carbon dioxide and sodium chloride. The substrate scope includes less activated aryl chlorides and carboxylates (>25 examples). The palladium loading could be reduced to 0.1 mol %, and Buchwald-style precatalysts could be used.